The behavior of geminate and diffusive radical caged-pairs arising from the photolysis of dicumyl ketone in conventional and supercritical carbon dioxide (SC-CO2) solvents has been examined. The results suggest that locally enhanced solvent density about a solute (solvent/solute clustering) can lead to an enhanced cage effect near the critical pressure in supercritical fluid solvents. This enhanced cage effect is similar in magnitude for both diffusive and geminate caged-pairs.